6, 7-phthaloylquinazoline vat dyestuffs and process of making same



Patented Oct. 10, 1950 K ai-rrfiinanoynoumazonms VAT DYE- STUFFS AND PROCESS OF MAKING Paul 'Sutte r,"Binningenfand Walter Kern, Sissach,

' Switzerland, assignors .to Ciba. Limited',-;'Basel, Switzerland, a Swiss firm No Drawin 'Application'jJanuary 11, 1949, Se-

rial No, 72,538. 1948 3 Claims: "(C1, 260-262) According ,to this invention valuable vat dyestuffs are madeby' reacting a a 4-halo'gen-6flphthaloyl-quinazoline', which contains as a substituent in the 2-position an aryl residue"containing at least two rings, with an amine'capableof being vatted.

The phthaloyl-quinazolines used as starting materials are new, but they can be prepared by methods in themselves knfownj. Especially advantageous is the methodforming the subject of patent application Serial No."'756,808, filed June 24, 1947, in which a 2-acylamino-anthraquinone- 3-nitrile is reacted, for example, with phosphorus pentachloride, whereby the quinaZoline ring is formed without the isolation of an intermediate product. 7

The above mentioned 6,7-phtha1oyl-quinazolines may with advantage contain chlorine as the halogen atom in the 4-position, and the aryl residue containing at least two rings and present in the 2-position may, for example, be wholly aromatic and contain exclusively aromatic six-membered carbon rings, The siX-membered carbon rings may be fused together or connected to each other by a simple carbo n-to-carb'on bond. 'As examples of such aryl residues there may be mentioned the residues of pyrene, chrysene, fluoranthene, phenanthrene and especiall residues having only two rings, for example, the residue of naphthalene or ofdiphenyl. I

Since the halogen'atom inthe 4-position of the quinazoline ring is reactive, the starting materials react easily with amines capable of being vatted. As vattable amines there come'into consideration, more especially, amines of the anthraquinone series such as l-aminothraquinone, in which the anthraquinone residue may contain substituents such as are usually present in known vat dyestuffs, especially alkoxy" groups, halogen atoms, acylamino and especially benzoylamino groups, or the like. It is of special advantage to use as vattable amines aminoanthraquinones Which contain fused-on rings, especially aminoanthraquinone- The reaction of the aforesaid halogen-quina zolines with vattable amines is advantageously conducted in a high boiling solvent or-diluent at a In Switzerland February 5,

Besides the high boiling solvents usually employed for reactions of this type, phenolmay in some cases be used with advantage.

The products of the invention are valuable vat dyestufis, and may bedescribed as fiff-phthaloylquinazolines which contain as a substituent in the l-position'the' residue of a vattable amine and as a substituent inthe 2-position an aryl residue" containing at least two rings. Of special importance are products which contain as a substituent in thee-position the residue of a 4-aminoanthra- The Vat dyestuffs of'the invention can be used- 7 for dyeingor printing bythe usual methods. Especially'valuable is the fact'that they dye with good absorption at moderate dyeing temperavat dyestuiis;

The following examples illustrate the-invention, 1

the parts and percentages being by weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same" as that of the kilogram to the liter:

Ezrample 1 8 parts of 2-diphenyl-4-chloro-6,'7+phthaloy1-- quinazoline of the formula and 6.1 parts of 4-aminoanthraquinone-2J Nlbenzacridone are heated in 200 parts of phenol for 1/2 at boiling temperature, ydrochloricacid Y being. given 01f. 200 partsof'pyridine are added,

' the whole is allowed to cool to'about'50" C., the precipitate is separated by filtering with suction,

. and the filter residue is washed with alcohol and dried. In this manner there is obtained in good raised temperature, for example, at 250 C. yield a green powder which dyes cotton from a U violet-brown vat strong yeliow greii tints of excellent fastness.

Similar dyestufis are obtained by using 4-aminoanthraquinone-2,l (N) benzacridones, which contain in the benz-nucleu a chlorine atom, for example, in the 4-, or G-position.

The above-mentioned 2-diphenyl-4-chloro-6,7- phthaloyl-quinazoline may be prepared by heating 2-(4-phenyl) -benzoylamino -3- cyananthraquinone of the formula I g ON in nitrobenzene with phosphorus .pentachloride It is a yellow-brown crystalline powder.

Example 2 6 parts of 2-(2'-naphthyl) -4-chloro-6.7-phthaloyl-quinazoline of the formula and 4.8 parts of 4- amino-2,1(N) -benzacridone are 7 heated 111150 parts of phenol for /2 hour at boiling temperature, hydrochloric acid being given ofi.

150 parts of pyridine are added, the whole is al- .lowed to cool to about 50? C., the precipitate is separated by filtering with suction, and the filter I :residue is washed with alcohol and dried. There .is obtained in good yield a dark green powder, I which dyes cotton from a violet-brown vat strong yellow-green tints of excellent fastness.

Similar dyestuffs are obtained by using 4-.

:amino anthraquinone -2,1 (N) benzacridones, which contain as a substituent in the benz-nucleus :a chlorine atom, for example in the 4-, 5V- or 6- position.

The chloro-6,7-phthaloyl-quinazoline may be .;pre-

pared by heating 2-(2'-naphthoyl)-amino-3-V cyan-anthraquinone of the formula 0 H NHOO...

in nitrobenzene with phosphorus "pentachloride.

It is a yellow-brown crystalline powder.

Example 3 1.5 parts-of the dyestufi obtained as described in Example 1 are vatted in 200 parts of water with the addition of 6 parts by volume of caustic soda solution of 36 B. and 3 parts of sodium hydrosulfite at about 60 C. The resulting stock vat 50 C and dyeing is carried on at that temperatime for 45 minutes. The cotton is then squeezed,

oxidized by exposure to air, rinsed, acidified and. again rinsed, and, if desired soaped at the boil. The cotton is dyed a fast yellow-green tint.

What we claim is: 1. A fiflfphthaloylquinazoline sponds to the formula which corre- ,quinonyl-2, ,(N) -benzacridone, and R stands for theradical of an aromatic hydrocarbon containing at least-wand at the most 18 carbon atoms and at least two and not more than four above mentioned 2-(2-naphthyl) -4-V is added to a dyebath which contains in 2800 7 parts of water 9 parts by volume of caustic. soda solution of 36 B. and 6 parts of sodium hydrosulfite. 100 parts of bleached cotton are entered at 40 C., 60 parts of sodium chloride are added after 15 minutes, the temperature is raised to 2. The yellowish green vat clyestufi of the 3. The yellowish green vat idyestuff' ;of the iormula I'PAUL SUTTER.

WALTER 1 7 "REFE EN S CITED The followingreferences are of record'in'the H file ofthis patent: 1

" UNITED STATES PATENTS 7 Number Name Y Date 2,187,81 Baum-ann'et a1. qai zaiigiq i i l 

1. A 6,7-PHTHALOYLQUINAZOLINE WHICH CORRESPONDS TO THE FORMULA 